Demonstration of Swensson’s NRRT.
\r\n\tTotal pelvic exenteration implies en bloc resection of the rectum, distal colon, bladder, lower ureter, internal reproductive organs, draining lymph nodes, and pelvic peritoneum. The procedure was first described by Brunschwig in 1948 as a palliative operation for advanced cervical cancer.
\r\n\r\n\t
\r\n\tDisease-free survival following salvage resection is dependent upon achieving an R0 resection margin. A clear understanding of applied surgical anatomy, appropriate preoperative planning, and a multidisciplinary approach to aggressive soft tissue, bony, and vascular resection with appropriate reconstruction is necessary.
\r\n\tThis book will discuss technical tips, tricks, and pitfalls that may assist in managing these cancers as well as the roles of additional boost radiation and intraoperative radiation therapy in the management of such cancers.
",isbn:"978-1-83881-103-7",printIsbn:"978-1-83881-102-0",pdfIsbn:"978-1-83881-117-4",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"6faf06dfe50a3febba931e41b794f4e5",bookSignature:"Dr. Alberto Vannelli",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/9788.jpg",keywords:"Colorectal Cancer, Pelvic Exenteration, Rectal Cancer, Cancer Recurrence, Colorectal Surgery, Chemotherapy, Target Therapy, Radiotherapy, Neoadjuvant and Adjuvant Therapies, Robotic Surgery, Prevention, Survival Rate",numberOfDownloads:873,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 27th 2020",dateEndSecondStepPublish:"June 17th 2020",dateEndThirdStepPublish:"August 16th 2020",dateEndFourthStepPublish:"November 4th 2020",dateEndFifthStepPublish:"January 3rd 2021",remainingDaysToSecondStep:"8 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:'Alberto Vannelli MD, was granted a Doctor of Medicine degree from "La Statale" University of Milan after which he did an internship and four year of residency in Liver Transplantation Unit at Maggiore Hospital (Milan). He completed in a residency in Colorectal Cancer Surgery at Fondazione IRCCS Istituto Nazionale dei Tumori of Milan. Since october 2018 he is Director of General Surgery at Valduce Hospital.',coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"34524",title:"Dr.",name:"Alberto",middleName:null,surname:"Vannelli",slug:"alberto-vannelli",fullName:"Alberto Vannelli",profilePictureURL:"https://mts.intechopen.com/storage/users/34524/images/system/34524.jpg",biography:"Alberto Vannelli obtained his Doctor of Medicine degree from “La Statale” University of Milan after which he did an internship and four years of residency in Liver Transplantation Unit at Maggiore Hospital (Milan). He completed a residency in Colorectal Cancer Surgery at Fondazione IRCCS Istituto Nazionale dei Tumori of Milan. He was an Attending Surgeon at Fondazione IRCCS Istituto Nazionale dei Tumori of Milan (2001- 2011) and Senior Attending Surgeon at Valduce Hospital at Como (2011- to date). Since October 2018, he is Director of General Surgery at Valduce Hospital. His practice is devoted to pelvic surgery with a particular interest in rectal cancer. Dr. Vannelli has contributed to the literature with an innovative theory on pelvic lymphedema and new modified tension-free technique in wall defects after abdominoperineal resection.",institutionString:"Ospedale Valduce",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"3",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"Ospedale Valduce",institutionURL:null,country:{name:"Italy"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:[{id:"73942",title:"Public Health: Prevention",slug:"public-health-prevention",totalDownloads:23,totalCrossrefCites:0,authors:[null]},{id:"74325",title:"Role of Magnetic Resonance Imaging in Patients with Rectal Cancer",slug:"role-of-magnetic-resonance-imaging-in-patients-with-rectal-cancer",totalDownloads:34,totalCrossrefCites:0,authors:[null]},{id:"73666",title:"Colorectal Cancer in Vietnam",slug:"colorectal-cancer-in-vietnam",totalDownloads:67,totalCrossrefCites:0,authors:[null]},{id:"73481",title:"Imaging and Diagnosis for Planning the Surgical Procedure",slug:"imaging-and-diagnosis-for-planning-the-surgical-procedure",totalDownloads:323,totalCrossrefCites:0,authors:[null]},{id:"73883",title:"Indocyanine Green Fluorescence in Colorectal Cancer",slug:"indocyanine-green-fluorescence-in-colorectal-cancer",totalDownloads:88,totalCrossrefCites:0,authors:[null]},{id:"73294",title:"Adjuvant Therapies in Colon Cancer",slug:"adjuvant-therapies-in-colon-cancer",totalDownloads:80,totalCrossrefCites:0,authors:[null]},{id:"73336",title:"Palliative Care in Colorectal Cancer",slug:"palliative-care-in-colorectal-cancer",totalDownloads:108,totalCrossrefCites:0,authors:[null]},{id:"73754",title:"Landscape of Current Targeted Therapies for Advanced Colorectal Cancer",slug:"landscape-of-current-targeted-therapies-for-advanced-colorectal-cancer",totalDownloads:30,totalCrossrefCites:0,authors:[null]},{id:"73584",title:"Laparoscopic Right Colectomy. Intracorporeal Anastomosis Is Associated with Better Outcome",slug:"laparoscopic-right-colectomy-intracorporeal-anastomosis-is-associated-with-better-outcome",totalDownloads:56,totalCrossrefCites:0,authors:[null]},{id:"73329",title:"Retinoids in Treatment of Colorectal Cancer",slug:"retinoids-in-treatment-of-colorectal-cancer",totalDownloads:66,totalCrossrefCites:0,authors:[null]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"301331",firstName:"Mia",lastName:"Vulovic",middleName:null,title:"Mrs.",imageUrl:"https://mts.intechopen.com/storage/users/301331/images/8498_n.jpg",email:"mia.v@intechopen.com",biography:"As an Author Service Manager, my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"1165",title:"Novel Strategies in Lymphedema",subtitle:null,isOpenForSubmission:!1,hash:"8d219d4509ab19a62d7dc15b39ac8ec9",slug:"novel-strategies-in-lymphedema",bookSignature:"Alberto Vannelli",coverURL:"https://cdn.intechopen.com/books/images_new/1165.jpg",editedByType:"Edited by",editors:[{id:"34524",title:"Dr.",name:"Alberto",surname:"Vannelli",slug:"alberto-vannelli",fullName:"Alberto Vannelli"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"6550",title:"Cohort Studies in Health Sciences",subtitle:null,isOpenForSubmission:!1,hash:"01df5aba4fff1a84b37a2fdafa809660",slug:"cohort-studies-in-health-sciences",bookSignature:"R. Mauricio Barría",coverURL:"https://cdn.intechopen.com/books/images_new/6550.jpg",editedByType:"Edited by",editors:[{id:"88861",title:"Dr.",name:"R. Mauricio",surname:"Barría",slug:"r.-mauricio-barria",fullName:"R. Mauricio Barría"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1591",title:"Infrared Spectroscopy",subtitle:"Materials Science, Engineering and Technology",isOpenForSubmission:!1,hash:"99b4b7b71a8caeb693ed762b40b017f4",slug:"infrared-spectroscopy-materials-science-engineering-and-technology",bookSignature:"Theophile Theophanides",coverURL:"https://cdn.intechopen.com/books/images_new/1591.jpg",editedByType:"Edited by",editors:[{id:"37194",title:"Dr.",name:"Theophanides",surname:"Theophile",slug:"theophanides-theophile",fullName:"Theophanides Theophile"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3161",title:"Frontiers in Guided Wave Optics and Optoelectronics",subtitle:null,isOpenForSubmission:!1,hash:"deb44e9c99f82bbce1083abea743146c",slug:"frontiers-in-guided-wave-optics-and-optoelectronics",bookSignature:"Bishnu Pal",coverURL:"https://cdn.intechopen.com/books/images_new/3161.jpg",editedByType:"Edited by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"371",title:"Abiotic Stress in Plants",subtitle:"Mechanisms and Adaptations",isOpenForSubmission:!1,hash:"588466f487e307619849d72389178a74",slug:"abiotic-stress-in-plants-mechanisms-and-adaptations",bookSignature:"Arun Shanker and B. Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"37771",title:"Surface Functionalization of Graphene with Polymers for Enhanced Properties",doi:"10.5772/50490",slug:"surface-functionalization-of-graphene-with-polymers-for-enhanced-properties",body:'\n\t\tGraphene, a single-atom-thick sheet of hexagonally arrayed sp2\n\t\t\t\t bonded carbon atoms, has been under the spotlight owning to its intriguing and unparalleled physical properties [1]. Because of its novel properties, such as exceptional thermal conductivity, [2] high Young’s modulus, [3] and high electrical conductivity,[4] graphene has been highlighted in fabricating various micro-electrical devices, batteries, supercapacitors, and composites [5, 7]. Especially, integration of graphene and its derivations into polymer has been highlighted, from the point views of both the spectacular improvement in mechanical, electrical properties, and the low cost of graphite [8, 9]. Control of the size, shape and surface chemistry of the reinforcement materials is essential in the development of materials that can be used to produce devices, sensors and actuators based on the modulation of functional properties. The maximum improvements in final properties can be achieved when graphene is homogeneously dispersed in the matrix and the external load is efficiently transferred through strong filler/polymer interfacial interactions, extensively reported in the case of other nanofillers. However, the large surface area of graphene and strong van der Waals force among them result in severe aggregation in the composites matrix. Furthermore, the carbon atoms on the graphene are chemically stable because of the aromatic nature of the bond. As a result, the reinforcing graphene are inert and can interact with the surrounding matrix mainly through van der Waals interactions, unable to provide an efficient load transfer across the graphene/matrix interface. To obtain satisfied performance of the final graphene/polymer composites, the issues of the strong interfacial adhesion between graphene–matrix and well dispersion of graphene should be addressed.
\n\t\t\tTo date, the mixing of graphene and functionalized graphene with polymers covers the most of the published studies, and the direct modification of graphene with polymers is a somewhat less explored approach. However, in many cases, to achieve stable dispersions of graphene and adequate control of the microstructure of the nanocomposites, non-covalent or covalent functionalization of graphene with polymers may be necessary. The non-covalent functionalization, which relies on the van der Waals force, electrostatic interaction or π-π stacking [10, 12], is easier to carry out without altering the chemical structure of the graphene sheets, and provides effective means to tailor the electronic/optical property and solubility of the nanosheets [13].\n\t\t\t\t The covalent functionalization of graphene derivatives is mainly based on the reaction between the functional groups of the molecules and the oxygenated groups on graphene oxide (GO) or reduced GO (r-GO) surfaces [14, 15],\n\t\t\t\t\t such as epoxides and hydroxyls on their basal planes and carboxyls on the edges [16].\n\t\t\t\t\t Compared with non-covalent functionalization, the covalent functionalization of graphene-based sheets holds versatile possibility due to the rich surface chemistry of GO/r-GO. However, it should be pointed out that the non-covalent or covalent attachment of graphene to polymer chains can improve some properties, but may be negative for others, especially those related to the movement of electrons or phonons. Although the functionalization of graphene with polymers is generally attempted with a view to conferring to the polymer new or improved properties, the polymer may also prevent the aggregation of the graphene sheets, where the graphene-polymer size ratio and molecular weight play important roles. For general bibliography on typical graphene-based nanocomposites, the reader can consult several monographs, reviews, and feature articles that summarize the state of the art of the field.
\n\t\t\tThe objective of the present work is to provide a broad overview on the methods developed to non-covalently or covalently bind graphene to polymers. The covalent linking of polymeric chains to graphene is at its initial stages and there is significant room for the development of new and improved strategies.
\n\t\tAs we know, GO is the main precursor for the functionalization of graphene with polymers. It is because that there are multiple oxygen-containing functionalities, such as hydroxyl, epoxy and carboxyl groups on GO sheets [16].\n\t\t\t\t\t GO is usually produced using different variations of the Staudenmaier [17] or Hummers \n\t\t\t\t[18] method in which graphite is oxidized using strong oxidants such as KMnO4, KClO3, and NaNO2 in the presence of nitric acid or its mixture with sulfuric \n\t\t\t\t[19, 20]. For more details about GO, we refer the reader to the extensive review of GO preparation, structure, and reactivity by Dreyer et al and Zhu et al. [19, 20].\n\t\t\t
\n\t\t\tFurthermore, the reduction of GO will remove most, but not all, of the oxygen-containing functionalities such as hydroxyl, carboxylic acid and epoxy groups. Therefore, some functionalization reactions are based on the reduced GO. Generally, GO can be exfoliated using a variety of methods, most commonly by solvent-based exfoliation and reduction in appropriate media or thermal exfoliation and reduction [16, 21]\n\t\t\t\t In the former route, the hydrophilic nature and increased interlayer spacing of GO facilitates direct exfoliation into solvents (water, alcohol, and other protic solvents) assisted by mechanical exfoliation, such as ultrasonication and/or stirring, forming colloidal suspensions of “graphene oxide”. The chemically reduced graphene oxide is produced by chemical reduction of the exfoliated graphene oxide sheets using hydrazine, [22, 24]\n\t\t\t\t dimethylhydrazine, [25] sodium borohydride followed by hydrazine, [26] hydroquinone, [ 27] vitamin C, [28]\n\t\t\t\t etc. However, the hazardous nature and cost of the chemicals used in reduction may limit its application. The most promising methods for large scale production of graphene is the thermal exfoliation and reduction of GO. Thermally reduced graphene oxide can be produced by rapid heating of dry GO under inert gas and high temperature [29, 31].\n\t\t\t\t Heating GO in an inert environment at 1050°C for 30 s leads to reduction and exfoliation of GO, producing low-bulk-density TRG sheets, which are highly wrinkled [32].\n\t\t\t\t In the thermal process, the epoxy and hydroxyl sites of GO decompose to produce gases like H2O and CO2, yielding pressures that exceed van der Waals forces holding the graphene sheets together, causing the occurrence of exfoliation.
\n\t\tIt is desirable that stronger bonds are usually formed between the graphene and the polymers by covalent functionalization of graphene with polymers. However, it is usually difficult to realize because ideal graphene lacks functional groups that can be conjugated with. In some cases, when the graphene sheets were exfiolated from GO, incomplete reduction process leaves oxygen-containing functionalities that are then available for further functionalizations. Other covalent functionalization strategies typically involve further disruption of the conjugation of the graphene sheets. Although covalent functionalization of graphene will compromise some of its natural conductivity, this method is still valuable in some cases when graphene’s other properties are desirable. More details of graphene functionalization via covalent bonds will be discussed below.
\n\t\t\tUntil now, “grafting to” and “grafting from” techniques have been developed to graft the polymer chains onto the graphene surface. The “grafting from” method relies on the immobilization of initiators at the surface of graphene, followed by in situ surface-initiated polymerization to generate tethered polymer chains. A number of studies of polymer-functionalized graphene by the “grafting from” method have been reported.
\n\t\t\t\tAmong the types of “grafting from“ polymerization [33, 46], \n\t\t\t\t\t ATRP is the most widely used, and represents the majority of the studies reported. ATRP is almost certainly chosen because it offers the advantages of radical polymerization, that is, a fast initiation process and the development of a dynamic equilibrium between dormant and growing radicals [47].\n\t\t\t\t\t In addition, a wide range of monomers can be polymerized by ATRP with controlled chain length. Moreover, block copolymers can be prepared by ATRP because of the living radical process. Furthermore, ATRP is probably the most practical technique for preparation of functional polymers because the terminal alkyl halide can be converted to a wide variety of functionalities by using conventional organic synthetic procedures.
\n\t\t\t\t\tSynthesis of surface-functionalized GO via attachment of an ATRP initiator (a-bromoisobutyryl bromide) followed by polymerization of styrene, butyl acrylate, or methyl methacrylate [38]. \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Lee et al. [38] have reported a new method for attaching polymer brushes to GO sheet using surface-initiated ATRP. The hydroxyl groups present on the surface of GO were first functionalized with a wellknown ATRP initiator (a-bromoisobutyryl bromide), and then polymers of styrene, butyl acrylate, or methyl methacrylate were grown directly via a surface-initiated polymerization (SIP) (Figure 1). The authors studied the case of polystyrene (PS) in detail and presented two main conclusions. First, they suggested that the polymer chain length can be tunable by changing the ratio of monomer and initiator modified GO. Second, they reported that the monomer loading can vary the molecular weight of the grafted PS, which was obtained by gel permeation chromatography (GPC) after detaching by saponification, and the polydispersity was low, which suggested the polymerization proceeds in a controlled manner. Furthermore, the PS-functionalized GO was shown to significantly increase the solubility in N,N-dimethylformamide (DMF), toluene, chloroform, and dichloromethane, improving the processing potential of these materials for applications in polymer composites.
\n\t\t\t\t\tFang et al. [43, 44] demonstrated the ability to systematically tune the grafting density and chain length of PS covalently bonded to graphene sheets by combining diazonium addition and ATRP. After reduction, r-GO was functionalized with 2-(4-aminophenyl) ethanol, reacted with 2-bromo-2-methylpropi-onyl bromide (BMPB), and subsequently the polymerization of styrene was carried out (Figure 2). Their results showed that the polydispersity of the high grafting density sample was more uniform than that of the low grafting density, which was attributed to the the degree of functionalization of r-GO sheets with the initiator because the diazonium coupling to graphene follows an identical radical mechanism as that for carbon nanotubes (CNTs). The relaxation of the polymer chains covalently bonded to the r-GO surface was strongly confined, particularly for segments in close proximity to the r-GO surface. This confinement effect could enhance the thermal conductivity of the polymer nanocomposites. The significant increases in thermal conductivity were observed for only 2.0 wt% functionalized r-GO in PS composites. Also, the resulting PS nanocomposites with 0.9 wt% functionalized r-GO revealed around 70% and 57% increases in tensile strength and Young’s modulus.
\n\t\t\t\t\tSynthetic routes for achieving controllable functionalization of graphene.\n\t\t\t\t\t\t\t\t\t 28\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Furthermore, Gonçalves et al. [40] developed the use of poly(methyl methacrylate) (PMMA) grafted from carboxylic groups in GO as a reinforcement filler. Here the BMPB initiators were immobilized by two esterification reactions: the carboxylic groups of GO were esterified with ethylene glycol, followed by reacting with BMPB using the same type of reaction as Lee et al. [38]. In this case, the polydispersity of the grafted PMMA, removed from the GO by hydrolysis, was found to be close to unity, once more suggesting a well-controlled process irrespective of the under estimated molecular weights. This PMMA-functionalized GO showed a good solubility in organic solvents such as chloroform and could be used as reinforcement filler in the preparation of PMMA composite films. Due to the strong interfacial interactions between the PMMA-functionalized GO and PMMA matrix caused by the presence of short PMMA chains covalently bonded to GO, an efficient load transfer from the GO to the matrix was formed, thus improving the mechanical properties of their nanocomposites, which were more stable and tougher than pure PMMA and its nanocomposites with unmodified GO (Figure 3). For example, addition of 1 wt% PMMA-functionalized GO clearly led to a significant improvement of the elongation at break, yielding a much more ductile and tougher material. In addition, the presence of PMMA-functionalized GO also stabilized the nanocomposites increasing the onset of thermal decomposition by around 50 °C.
\n\t\t\t\t\tLoad-displacement nanoidentation (left) and stress-strain curves (right) of films of PMMA and its nanocomposites with PMMA-functionalized graphene. 40\n\t\t\t\t\t\t\t
Yang et al. [42] also took advantage of the carboxylic groups to graft poly-(2-dimethylaminoethyl methacrylate) (PDMAEMA) onto GO sheets. Here, the BMPB initiators were attached onto GO sheets by two steps involving amidation reactions. This functionalization of GO with PDMAEMA not only enhanced the solubility in acidic aqueous solutions (pH = 1), but also in short chain alcohols. Moreover, this solubility allowed this functionalized-GO to be mixed with spherical particles of poly(ethylene glycol dimethacrylate-co-methacrylic acid) to generate decorated GO sheets.
\n\t\t\t\tBesides the ATRP method, polycondensation, [33] ring opening polymerization [34], reversible addition-fragmentation chain transfer (RAFT) mediated mini-emulsion polymerization [35],\n\t\t\t\t\t\t direct electrophilic substitution [36], and Ziegler–Natta polymerization [37] have also been used to functionalize the graphene sheets with various polymer chains, which will be discussed below.
\n\t\t\t\t\tWang et al. [33] functionalized GO sheets with polyurethane (PU) by using the polycondensation method. Here GO sheets were reacted with 4,4’-diphenylmethane diisocyanate followed by polycondensation of poly(tetramethylene glycol) and ethylene glycol. The presence of PU chains linked to GO remarkably improved the dispersion of GO in PU matrix, which was confirmed by the morphological study, and make it compatible with pure PU forming strong interfacial interactions that provide an enhanced load transfer between the matrix and the GO sheets thus improving their mechanical properties, as well as their thermal properties. With the incorporation of 2.0 wt% PU-functionalized GO, the tensile strength and storage modulus of the PU nanocomposites increased by 239% and 202%, respectively (Figure 4). Furthermore, the nanocomposites displayed high electrical conductivity, and improved thermal stability of PU was also achieved (Figure 4).
\n\t\t\t\t\tThe improved thermal and mechanical propertied of PU/GO nanocomposites [33].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Etmimi et al. [35] investigated the preparation of PS/GO nanocomposites via RAFT mediated mini-emulsion polymerization. In this process, dodecyl isobutyric acid trithiocarbonate (DIBTC) RAFT agent was attached to the hydroxyl groups of GO through an esterification reaction (Figure 5). The resultant RAFT-grafted GO was used for the preparation of PS/GO nanocomposites in miniemulsion polymerization. The stable miniemulsions were obtained by sonicating RAFT-grafted GO in styrene monomer in the presence of a surfactant, followed by polymerizing using AIBN as the initiator to yield encapsulated PS-GO nanocomposites. The molecule weight and polydispersity of PS in the nanocomposites depended on the amount of RAFT-grafted GO in the system, in accordance with the features of the RAFT polymerization method. The thermal stability of the obtained PS/GO nanocomposites was improved, which may be attributed to the intercalation of PS into the lamellae of graphite. Furthermore, the increased RAFT-grafted GO significantly resulted in the improved mechanical properties of the nanocomposites. The storage and loss modulus of the nanocomposites were higher than those of the standard PS when the GO loadings reached 3 and 6%, respectively. Oppositely, as RAFT-grafted GO content increased, the Tg values of the sample decreased. This was attributed to the change in the molecule weight of the PS chains in the nanocomposites.
\n\t\t\t\t\tThe overall synthesis route for the preparation of RAFT immobilized GO nanosheets [35].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Fabrication of PP/GO nanocomposites by in situ Ziegler-Natta polymerization [37].\n\t\t\t\t\t\t\t
Huang et al. [37] reports the first example of preparation of polypropylene/GO (PP/GO) nanocomposites via in situ Ziegler−Natta polymerization. As illustrated in Figure 6, a Mg/Ti catalyst species was immobilized onto GO sheets by reacting with the surface functional groups including −OH and −COOH. Subsequent propylene polymerization led to the in situ formation of PP matrix, which was accompanied by the nanoscale exfoliation of GO. Independent of the opposing nature of the polymer and GO, a good dispersion of GO sheets in PP matrix was observed, which was verified by morphological examination through TEM and SEM observation. Furthermore, high electrical conductivity was discovered with thus prepared PP/GO nanocomposites, this being the only paper reporting conductive materials prepared by grafting a polymer from graphene sheets. For example, at a GO loading of 4.9 wt %, σc was measured at 0.3 S m−1. We believe that this must originate from a side reaction involving the reduction of GO sheets that occurs in one of the synthetic steps.
\n\t\t\t\t\t\n\t\t\t\tUltrasound has found important applications in a diverse range of materials and chemical syntheses [48, 51].\n\t\t\t\t\t\t Both the physical and chemical effects of ultrasound arise from acoustic cavitation: the formation, growth, and collapse of bubbles in liquids irradiated with high intensity ultrasound [48 - 50, 52].\n\t\t\t\t\t\t Localized hot spots with temperature of ~5000K and pressures of hundreds of bars are generated during the bubble collapse within liquid, which can induce some chemical reactions that can’t take place under normal conditions. Xu et al. [53]\n\t\t\t\t\t\t reported a convenient single-step sonication-induced approach for the preparation of polymer functionalized graphenes from graphite flakes and a reactive monomer, styrene. In this work, they showed that by choosing a reactive medium as the solvent, the combined mechanochemical effects of high intensity ultrasound can, in a single step, readily induce exfoliation of graphite to produce functionalized graphenes. Ultrasonic irradiation of graphite in styrene results in the mechanochemical exfoliation of graphite flakes to single-layer and few-layer graphene sheets combined with functionalization of the graphene with PS chains (Figure 7). The PS chains are formed from sonochemically initiated radical polymerization of styrene. They also tested a variety of other solvents, including toluene, ethylbenzene, 1-dodecene, and 4-vinylpyridine to prepare functionalized graphenes. Only the easily polymerizable reactants containing vinyl groups, styrene and 4-vinylpyridine, lead to stable functionalized graphene. Such functionalized graphene have good stability and solubility in common organic solvents and have great potential for graphene-based composite materials.
\n\t\t\t\t\tMoreover, direct photografting reactions of vinyl monomers came into focus for the preparation of stable polymer brushes. Two approaches in particular, the sequential “living” photopolymerization and the self-initiated photografting and photopolymerization (SIPGP), attracted the attention of numerous research groups because of the facile preparation and broad applicability. Steenackers et al. \n\t\t\t\t\t\t[54] showed that PS chains could covalently bound to graphene by the UV-induced polymerization of styrene (Figure 8). Photopolymerization occurs at existing defect sites and that there is no detectable disruption of the basal plane conjugation of graphene. This method thus offers a route to define graphene functionality without degrading its electronic properties. Furthermore, photopolymerization with styrene results in self-organized intercalative growth and exfoliation of few layer graphene sheets. Under these reaction conditions, a range of other vinyl monomers exhibits no reactivity with graphene. However, the authors demonstrate an alternative route by which the surface reactivity can be precisely tuned, and these monomers can be locally grafted via electron-beam-induced carbon deposition on the graphene surface.
\n\t\t\t\t\tExperimental setup of the one-step mechanochemical process for exfoliation of graphite and sonochemical functionalization of graphene [53].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Patterned polymer brush layers on CVD-grown single layer graphene are prepared by UV illumination through a mask in bulk styrene. Surface photopolymerization occurs selectively in illuminated regions of the material [54].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
The preparation of PVAc grafted GO by γ-ray irradiation-induced graft polymerization [55].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
γ-ray radiation-induced graft polymerization has many advantages, including being a single-step chemical reaction, needing no additives or catalysts, being conducted at room temperature, cost-effective, and so on. Above all, it is versatile for vinyl monomers that undergo free radiation polymerization, and production can be easily scaled-up. Zhang et al. [55] \n\t\t\t\t\t\t reported a facile approach to functionalize GO sheets with poly(vinyl acetate) (PVAc) by γ-ray irradiation-induced graft polymerization (Figure 9). Due to the full coverage of PVAc chains and solvated layer formation on GO sheets surface, which weakens the interlaminar attraction of GO sheets, PVAc-functionalized GO was well dispersed in common organic solvents, and the dispersions obtained were extremely stable at room temperature without any aggregation.
\n\t\t\t\t\t\n\t\t\t\t\tFurthermore, Lee at al. [56] have developed a method to selectively fluorinate graphene by irradiating fluoropolymer-covered graphene with a laser (Figure 10). Here the sp2-hybrized graphene would react with the active fluorine radicals, which was produced by photon-induced decomposition of the fluoropolymer under laser-irradiation, and form C-F bonds. However, this reaction only occurred in the laser-irradiated region. The kinetics of C–F bond formation is dependent on both the laser power and fluoropolymer thickness. Furthermore, the resistance of the graphene dramatically increased due to the fluorination, while the basic skeletal structure of the carbon bonding network is maintained. This is an efficient method for isolating graphene devices because the laser irradiation on fluoropolymer-covered graphene process produces fluorinated graphene with highly insulating properties in a single step.
\n\t\t\t\t\tThe scheme showing a mechanism for fluorination under laser-irradiation.56\n\t\t\t\t\t\t\t
As commented previously, the “grafting from” method relies on the immobilization of initiators at the surface of graphene, followed by in situ surface-initiated polymerization to generate tethered polymer chains. However, this may not be possible in certain cases, where the covalent linkage between the presynthesized polymer and graphene emerges as the only alternative. In order to expand the type of polymers that can be bound to graphene, the category of “grafting-to” method can be employed to achieve this purpose. The “grafting to” technique involves the bonding of preformed end functionalized polymer chains to the surface of graphene. Therefore, the prepared graphene require adequate functional groups, which could react with specific polymers. Or the polymer has functionalities capable of reacting with either graphene or its chemically broader cousin, GO. In the following part, we will summarize the type of reactions and the families of polymers that have been grafted to the graphene.
\n\t\t\t\tEsterification/amidation reactions between carboxylic groups in GO and hydroxyl or amine groups in the polymer have been widely investigated [14, 15, 44, 57, 60].\n\t\t\t\t\t\t\t In this respect, poly(vinyl alcohol) (PVA) was covalently bonded to GO [14, 57] and r-GO [14]\n\t\t\t\t\t\t by using a typical catalytic system for esterification (Figure 11). After functionalization with PVA chains, the solution processability of graphene was significantly improved. And the degree of functionalization was shown to be low, probably due to steric hindrance caused by the huge volume of GO. However, due to the presence of the huge graphene sheets, significant changes in the crystalline properties as well as in the tacticity of the polymer were observed. The originally semicrystalline PVA became completely amorphous, and the Tg increased by 35 °C after bonded to GO sheets. The decrease in crystallinity was attributed to the intercalation of PVA chains between the graphene sheets as well as the formation of “secondary” bonds, for example, hydrogen bonding that breaks intra- and interchain bonds. Finally, it has been demonstrated that the reaction is favoured at specific conformations at the isotactic sequences where the hydroxyl groups are more exposed (lower internal steric hindrance) than in the syndiotactic counterpart.
\n\t\t\t\t\tSchematic Illustration of the Esterification of GO with PVA [14].\n\t\t\t\t\t\t\t
A similar strategy has been approached to functionalize r-GO with poly(vinyl chloride) (PVC) [59].\n\t\t\t\t\t\t In this step, the susceptible groups in PVC chains could react with the functional groups on r-GO sheets by esterification, which was provided by a nucleophilic substitution reaction [61, 62]. \n\t\t\t\t\t\t Furthermore, several methodologies to prepare r-GO/PVC nanocomposites and the optimum conditions have been established. The covalent attachment of r-GO to appropriately functionalized PVC is the only effective method to produce nanocomposites with improved thermal and mechanical properties (Figure 12). The absolute values of the mechanical and thermal properties of PVC-functionalized GO nanocomposites are higher than those for a similar system using MWNTs as reinforcement because of the higher aspect ratio of the r-GO sheets with respect to the MWNTs. The introduction of r-GO also increases the Tg of the composites, reflecting the changes in the mobility of the PVC chains. However, due to the lower strength of the “secondary bonds”, such as halogen bonding and hydrogen bonding for PVC and PVA respectively, the changes in Tg for PVC were much lower than those reported for PVA, which had a similar degree of functionalization with PVC-functionalized GO. The existence of these secondary bonds can lead to some additional ordering that alters the segmental mobility and consequently the final properties.
\n\t\t\t\t\tComparison of (a) storage modulus and (b) tan δ curves for neat PVC (square), PVC functionalized CNTs (triangle), PVC functionalized GO (solid circle), and PVC functionalized r-GO (open circle) [59].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Furthermore, conjugated polymer-functionalized graphene materials have also been prepared by esterification/amidation reactions [60, 63].\n\t\t\t\t\t\t In these cases, the ends of the conjugated polymers were bonded to the functional groups on the graphene sheets. As a result, the solubility of the obtained functionalized graphene was significantly improved in common solvents, enabling device preparation by solution processing. Thus, GO functionalized with both triphenylamine-based polyazomethine-modified GO (TPAPAM-GO) and poly(3-hexylthiophene) modified GO (P3HT-GO) (Figure 13) can be incorporated into specific devices by simple spin coating to obtain composites that exhibit non-volatile memory effect as well as higher power conversion efficiency for solar cells, demonstrated in the cases of TPAPAM-GO and P3HT-GO, respectively.
\n\t\t\t\t\tSynthesis procedure for chemical grafting of CH2OH-terminated P3HT chains onto graphene, which involves the SOCl2 treatment of GO (step 1) and the esterification reaction between acyl-chloride functionalized GO and MeOH-terminated P3HT (step 2) [47].\n\t\t\t\t\t\t\t
Nitrene chemistry, an approach used to functionalize graphene with single molecules [64, 65], \n\t\t\t\t\t\t has also been extended to polymers [66, 67].Nitrene chemistry is a versatile tool that allows the functionalization of graphene with a pool of functionalities, potentiating graphene solubility, and dispersion in a wide variety polymeric matrices. By using of this technology, He and Gao [67]\n\t\t\t\t\t have reported a general and versatile approach to graft of polymers onto graphene sheets. In their experiment, a wide range of immobilized functional groups were used to graft specific polymers from it (Figure 14). Though the cycloadditions of nitrene radicals and thermal reduction of GO occurs simultaneously, the conductivity of graphene diminished after functionalization, values of around 300-700 S/m for PS and poly(ethylene glycol) (PEG)-functioanlzied graphene were obtained. This was mainly due to the high amounts of graphene in the final product, which is reasonable because although the polymer is linked to graphene by the ends, the molecular weight of the polymers is low, making the mass percentage of graphene high.
\n\t\t\t\t\tGeneral strategy for the preparation of functionalized graphene sheets by nitrene chemistry and the further chemical modifications [67].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Besides the methods mentioned above, other “grafting to” approaches have also been investigated, such as the opening of maleic rings in maleic acid (MA) grafted polyethylene by amine functionalized graphene [68],\n\t\t\t\t\t\t nucleophilic epoxy-ring opening in GO by amine groups in biocompatible poly-l-lysine [69],\n\t\t\t\t\t\t atom transfer nitroxide radical coupling (ATNRP) of PNIPAM and 2,2,6,6-tetramethylpiperidine-1-oxyl-modified graphene [70],\n\t\t\t\t\t\t\t\n\t\t\t\t\t\t and simultaneous reduction of GO and radical grafting of PMMA by phase transfer [71].\n\t\t\t\t\t\t\n\t\t\t\t\t
\n\t\t\t\tShen et al. [72] have reported PVA-functionalized graphene (f-G) could be prepared by ultrasonication of pristine graphene (p-G) in a PVA aqueous solution (Figure 15). Ultrasonic irradiation of graphene can cause a considerable amount of defects on the graphene surface, which might produce reactive sites in situ as a result of the high temperature and pressure during bubble collapse. Moreover, the original defects on pristine graphene can also be easily destroyed and produce reactive sites during ultrasonic irradiation. The PVA chain radicals produced by sonochemical degradation of the PVA solution can react easily with graphene, because of the reactive sites formed on the graphene surface, and readily functionalized them via “grafting to” method. The content of PVA on graphene was estimated to be ~35%. The f-G could be well dispersed in the PVA matrix by a simple solution mixing and casting procedure. Due to the effective load transfer between f-G and PVA matrix, the mechanical properties of the f-G/PVA films were significantly improved. Compared with the p-G/PVA films, a 12.6% increase in tensile strength and a 15.6% improvement of Young’s modulus were achieved by addition of only 0.3 wt% f-G. Moreover, this simple ultrasonication technique could enable us to functionalize graphene with other polymers.
\n\t\t\t\t\tSchematic illustration of the sonochemical preparation process of PVA-functionalized graphene [72].\n\t\t\t\t\t\t\t
As a summary, “grafting-to” methods are highly versatile since they take advantage of the chemistry of GO that can be appropriately modified with a wide variety of functional groups providing a capacity for reaction with almost any type of polymers. In addition, “grafting-to” method allows the selection of the location of graphene, that is, at the end or as part of the main chain that can be directly related to changes in the final properties.
\n\t\t\t\tAs shown in the aforementioned examples, the covalent functionalization of polymers on graphene-based sheets holds versatile possibility due to the rich surface chemistry of GO/r-GO. Nevertheless, the non-covalent functionalization, which almost relies on hydrogen bonding or π–π stacking, is easier to carry out without altering the chemical structure of the capped r-GO sheets, and provides effective means to tailor the electronic/optical property and solubility of the nanosheets. The first example of non-covalent functionalization of r-GO sheets was demonstrated by the in situ reduction of GO with hydrazine in the presence of poly(sodium 4-styrenesulfonate) (PSS) [12], in which the hydrophobic backbone of PSS stabilizes the r-GO, and the hydrophilic sulfonate side groups maintains a good dispersion of the hybrid nanosheets in water.
\n\t\t\tπ–π stacking interactions usually occur between two relatively large non-polar aromatic rings having overlapping π orbitals. They can be comparable to covalent attachment in strength and hence provide more stable alternatives to the weaker hydrogen bonding, electrostatic bonding and coordination bonding strategies. Furthermore, π–π stacking functionalization does not disrupt the conjugation of the graphene sheets, and hence preserves the electronic properties of graphene.
\n\t\t\t\tIn order to functionalize graphene with polymers via π–π stacking, one strategy is for the polymer chains to be synthesized with pyrene moieties as the termini of the polymer chains. RAFT polymerization can be a useful tool to achieve this aim. Polymers with pyrene end-groups have been made using RAFT mechanism in several recent papers [73, 80].\n\t\t\t\t\t\t\n\t\t\t\t\t\t\n\t\t\t\t\t
\n\t\t\t\t\tA schematic depicting the synthesis of pyrene-terminated PNIPAAm using a pyrene-functional RAFT agent and the subsequent attachment of the polymer to graphene [ 81].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Liu et al. synthesized thermoresponsive graphene-polymer nanocomposites. They first took advantage of RAFT polymerization to synthesize a well-defined thermoresponsive pyrene terminated poly(N-isopropylacrylamide) (PNIPAAm), followed by attachment onto the basal plane of graphene sheets via π-π stacking interactions (Figure 16) [81].\n\t\t\t\t\t\t The lower critical solution temperature (LCST) of pyrene-terminated PNIPAAm was measured to be 33 ° C. However, after the pyrene-functional polymer functionalized with graphene sheets, the resultant graphene composites were also thermoresponsive in aqueous solutions, but with a lower LCST of 24 °C.
\n\t\t\t\t\tSimilarly, Liu et al. also prepared pH sensitive graphene-polymer composites by functionalization of graphene with a pyrene-terminated positive charged polymer, poly(2-N,N‘-(dimethyl amino ethyl acrylate)) (PDMAEA), and a negatively charged polymer, polyacrylic acid (PAA) [80].\n\t\t\t\t\t During the process, a pyrene-terminated RAFT agent was used to prepare the pyrene-terminated PDMAEA and PAA. When manipulating the pH of the graphene−composite suspensions, phase transfer between the aqueous and organic phases was observed. Self-assembly of the two oppositely charged graphene-polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements (Figure 17). In addition to RAFT mechanism, π-orbital rich polymers have also been synthesized by using of ATRP method for functionalization of r-GO to afford the fluorescent and water-soluble graphene composites via π-π stacking interactions [82].\n\t\t\t\t\t
\n\t\t\t\t\tSynthesis of pH sensitive pyrene-polymer composites via π-π stacking interactions for the self-assembly of functionalized graphene into layered structures [80].\n\t\t\t\t\t\t\t
Moreover, conjugated polyelectrolytes with various functionalities have been used to modify r-GO nanosheets [83 - 85], in the hope to achieve good solubility in different kinds of solvents, and at the same time acquire added optoelectronic properties. Qi et al. has specially designed an amphiphilic coil–rod–coil conjugated triblock copolymer (PEG-OPE, chemical structure shown in Figure 18A) to improve the solubility of graphene-polymer nanocomposites in both high and low polar solvents [33, 83]. In the proposed configuration, the conjugated rigid-rod backbone of PEG-OPE can bind to the basal plane of the r-GO via the π-π stacking interaction (Figure 18B), whereas the lipophilic side chains and two hydrophilic coils of the backbone form an amphiphilic outer-layer surrounding the r-GO sheet. As a result, the obtained r-GO sheets with a uniformly coated polymer layer (Figure 18C) are soluble in both organic low polar (such as toluene and chloroform) and water-miscible high polar solvents (such as water and ethanol).
\n\t\t\t\t\tA) Chemical structure of PEG-OPE. (B) Schematic illustration of fabrication of PEG-OPE stabilized r-GO sheets. (C) Tapping-mode AFM image and cross-sectional analysis of PEG-OPE-r-GO on mica [67].\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
A) Chemical structure of the newly designed PFVSO3. B) Schematic illustration of the synthesis of PFVSO3-stabilized r-GO in H2O: step 1, oxidative treatment of graphite (gray-black) yields single-layer GO sheets (brown); step 2, chemical reduction of GO with hydrazine in the presence of PFVSO3 produces a stable aqueous suspension of PFVSO3-functionalized r-GO sheets (PFVSO3-r-GO). C) Photograph of aqueous dispersions of GO (i), r-GO (ii), PFVSO3-r-GO (iii), and PFVSO3 (iv) [84]. \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
In another study, Qi et al. demonstrated the preparation of highly soluble r-GO hybrid material (PFVSO3-r-GO) by taking advantage of strong π–π interactions between the anionic CPE and r-GO (Figure 19) [84]. The resulting CPE-functionalized r-GO (PFVSO3-r-GO) shows excellent solubility and stability in a variety of polar solvents, including water, ethanol, methanol, dimethyl sulfoxide, and dimethyl formamide. The morphology of PFVSO3-r-GO is studied, which reveal a sandwich-like nanostructure. Within this nanostructure, the backbones of PFVSO3 stack onto the basal plane of r-GO sheets via strong π–π interactions, while the charged hydrophilic side chains of PFVSO3 prevent the rGO sheets from aggregating via electrostatic and steric repulsions, thus leading to the solubility and stability of PFVSO3-rGO in polar solvents. Furthermore, the presence of PFVSO3 within r-GO induces photoinduced charge transfer and p-doping of r-GO. As a result, the electrical conductivity of PFVSO3-r-GO is not only much better than that of GO, but also than that of the unfunctionalized r-GO.
\n\t\t\t\tHigh temperature and strong shear forces are usually involved during the melt blending process, which tends to fracture the nanoparticle aggregates, and endow polymer chains with the ability to diffuse into the gaps of the nanoparticle interlayer. Furthermore, as suggested by theoretical and experimental studies [86, 87]\n\t\t\t\t\t\t chemical or physical interactions can be formed between the fillers and the polymer components. Zhang et al [88] found the melt blending led to enhanced interactions between PS and CNTs, which was indicated by increased amount of PS linked to CNTs and therefore dramatically increased solubility of CNTs in some solvents. Taking advantage of this method, Zhou et al [89]\n\t\t\t\t\t\t obtained PS-coated CNTs through simple melt mixing of PS with CNTs. Furthermore, Lu et al [90]\n\t\t\t\t\t\t studied the styrene-butadiene-styrene tri-block copolymer (SBS)/CNTs composite, and their results showed that there were interactions between CNTs and SBS occurred during melt mixing, leading to an improvement of the mechanical properties of SBS/CNTs composites, as well as the homogeneous dispersion of CNTs in SBS. The mechanism of melt blending on these enhanced interactions was mainly attributed to the formation of π-π stacking between the aromatic system of π-electrons of PS and the π-electrons system of CNTs during melt blending [10, 88].\n\t\t\t\t\t\t\n\t\t\t\t\t
\n\t\t\t\t\t\n\t\t\t\t\tMelt Blending can also graft PS chains onto the surface of graphene sheets via π-π interactions. The interaction between graphene and PS was significantly enhanced by melt blending, which led to an increased amount of PS-functional graphene (PSFG) exhibiting good solubility in some solvents [10]. The mechanism for the in-situ formation of π-π stacking was addressed, as illustrated in Figure 20. It was proposed that the strong shear action applied by extruder could stretch the PS chains and endow the polymer chains with possibility to diffuse into the interlayer gap of graphene sheets. Moreover, the PS chains could be pushed towards to graphene sheets to form the π-π stacking under high shear forces. The UV-vis absorption spectroscopy of PSFG presented an obvious red shift, suggested the presence of π-π stacking between PS and graphene.
\n\t\t\t\tSchematic for the forming of π-π stacking in the process of melt blending [10].\n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t
Hydrogen bonding is very common in the biological world. An individual hydrogen bond is not very strong (2–8 kcal/mol); however, multiple hydrogen bonds will afford strong interactions as seen in DNA hybridization. Liang et al. prepared PVA nanocomposites with graphene by dispersing GO sheets into PVA matrix at molecular level [91]. The authors considered that the increased tensile strength and Young\'s modulus of the PVA/GO composite films were caused by the strong hydrogen bonding interactions between the residual oxygen-containing groups of GO sheets, such as epoxides and hydroxyls on their basal planes and carboxyls on the edges, and hydroxyl groups of the PVA chains. Polymer/graphene nanocomposites with other hydrophilic polymers, epoxy, poly(acrylonitrile) and polyaniline exhibited extraordinary high increase in modulus or glass transition temperature, attributed to hydrogen bonding interactions [92 - 94].\n\t\t\t\t\t\t\n\t\t\t\t\t\n\t\t\t\t
\n\t\t\tThe use of graphene or functionalized graphene materials usually exploits properties such as the large surface area or high electrical conductivity. Currently, the applications of functionalized graphene are focused on clean energy devices and electronic devices, as well as on sensors, medical devices and catalysis. Two examples will be discussed below.
\n\t\t\t\n\t\t\tNon-covalent chemical modification between functionalized pyrene and graphene was adopted to achieve patterned arrays of glucose oxidase (GOD) for potential applications in glucose sensors, cell sensors and tissue engineering [96].\n\t\t\t\t In research by Zeng et al. as illustrated in Figure 21, [95]\n\t\t\t\t\t\n\t\t\t\t chemically reduced GO was functionalized by pyrene-grafted poly(acrylic acid) (PAA) in aqueous solution on the basis of π-π stacking as well as van der Waals interactions. Then PAA-functionalized graphene (PAA-graphene) was LbL assembled with poly(ethyleneimine) (PEI). Graphene multilayer films facilitated the electron transfer, enhancing the electrochemical reactivity of H2O2. On the basis of this property, they fabricated a bienzyme biosensing system for the detection of maltose by successive LbL assembly of functionalized graphene, GOD, and glucoamylase (GA), which showed great promise in highly efficient sensors and advanced biosensing systems.
\n\t\t\tSchematic Illustration of the Strategies for layer-by-layer assembly of graphene multilayer films for enzyme-based glucose and maltose biosensing [95].\n\t\t\t\t\t\n\t\t\t\t\t
Schematic illustration of the electron-withdrawing from graphene by PDDA to facilitate the ORR process [97].\n\t\t\t\t\t
The planar structure and superb conductivity of graphene also provide an appropriate platform for novel electrochemical sensors. A metal-free electrocatalyst for the oxygen reduction reaction (ORR) was achieved with graphene sheets functionalized with an electron acceptor, poly(diallyldimethylammonium chloride) (PDDA) (Figure 22). The resultant positively charged graphene composite was demonstrated to show remarkable electrocatalytic activity toward ORR with better fuel selectivity, tolerance to CO poisoning, and long-term stability than that of the commercially available Pt/C electrode [97].\n\t\t\t\t\n\t\t\t The observed ORR electrocatalytic activity induced by the intermolecular charge-transfer provides a general approach to various carbon-based metal-free ORR catalysts for oxygen reduction.
\n\t\t\t\n\t\tGenerally speaking, functionalization of graphene with polymers can be achieved via either covalent or non-covalent interactions. Furthermore, the functionalization of graphene is always based on the graphene from previously prepared GO, which has multiple oxygen-containing functionalities, such as hydroxyl and carboxyl groups. In the covalent functionalizations, “grafting to” and “grafting from” techniques have been developed to graft the polymer chains onto the graphene surface. The “grafting from” method relies on the immobilization of initiators at the surface of graphene, followed by in situ surface-initiated polymerization to generate tethered polymer chains. The “grafting to” technique involves the bonding of preformed end functionalized polymer chains to the surface of graphene. Comparing both methods through the examples described above, it seems that “grafting-to“ method allows the covalent bonding of a wider variety of polymers to graphene. The polymers “grafted from“ graphene are those produced principally by some type of radical polymerization, such as ATRP and RAFT. However, the most relevant polymers grafted from graphene, such as PS and PMMA have also been attached to graphene by the “grafting-to“ method. In principle, for polymers obtained by ATRP the “grafting-from“ method might be the most appropriate, but this depends on the features desired in the final composite, because through “grafting to“ method graphene forms part of the bulk polymer whereas in the “grafting from“ it is limited to a terminal group. Moreover, except for a few exceptions, functional polymers and polymers synthesized by condensation reactions are principally bound to graphene by the grafting-to approach. Regarding to use PVA and PVC to functionalize graphene, we select the “grafting to“ method due to the experimental procedures employed to obtain these polymers. In fact, it is well known that PVA is not prepared by polymerization of the corresponding monomer, and the majority of PVC is synthesized by free-radical polymerization through suspension or bulk processes. Finally, radiation-induced graft polymerization has been utilized in the “grafting to” and “grafting from” techniques, due to its advantages, including being a single-step chemical reaction, needing no additives or catalysts, being conducted at room temperature, cost-effective, and so on.
\n\t\t\tThe covalent functionalization of polymers on graphene-based sheets holds versatile possibility due to the rich surface chemistry of GO/r-GO. Nevertheless, the non-covalent functionalization, which almost relies on hydrogen bonding or π-π stacking, is easier to carry out without altering the chemical structure of the capped rGO sheets, and provides effective means to tailor the electronic/optical property and solubility of the nanosheets. π-π stacking interactions usually occur between two relatively large non-polar aromatic rings having overlapping π orbitals. In order to functionalize graphene with polymers via π-π stacking, one strategy is for the polymer chains to be synthesized with pyrene moieties as the termini of the polymer chains. Moreover, conjugated polyelectrolytes with various functionalities have been used to functionalize graphene via π-π stacking. The hydrogen bonding interactions between the residual oxygen-containing groups of graphene sheets and hydroxyl groups of the hydrophilic polymer chains, such as PVA chains, have also been used to functionalize the graphene in order to obtain increased tensile strength and Young\'s modulus.
\n\t\tData reliability is a common concern across all studies that use surveys, but more so while asking sensitive questions. Sensitive questions include sacred, private, or potentially exposing information that could be incriminating or discriminating for a respondent, or for the social group that is represented by the respondent [1]. For example, in studies which evaluate exposure to HIV infection, respondents are often asked sensitive questions regarding their opposite- or same-sex sexual practices. As another example, in studies which aim to assess substance use and abuse, respondents might suppress disclosure of their drug and alcohol misuse to avoid embarrassment or potentially harmful/unwanted consequences. Estimating the prevalence of such sensitive attributes is particularly important for health care researchers to build scientific knowledge, create necessary public health interventions, and develop political strategies.
\nTwo problems typically arise while studying sensitive topics, (1) nonresponse rate increase and (2) social desirability bias (SDB), which is defined as the tendency of answering questions in a socially acceptable fashion rather than answering truthfully, occurs. Nonresponse rates can be reduced by utilizing some strategies such as using advance letters, offering incentives, using more experienced interviewers, and making the topic salient to respondents [2, 3, 4, 5, 6]. However, if these strategies are more effective for some particular subpopulations compared to others, a reduction in nonresponse can in reality increase nonresponse bias. Statistical techniques can also be used to minimize the effects of unit nonresponse after the data is collected [7]; yet, none of these approaches can prevent SDB.
\nMany researchers have suggested using self-administered modes such as mail, web, computer-assisted self-interviewing (CASI), audio computer-assisted self-interviewing (ACASI), telephone audio computer-assisted self-interviewing (T-ACASI), or touchtone data entry (TDE) in order to reduce SDB [8, 9, 10, 11]. However, self-administered modes have their own drawbacks. For example, all self-administered surveys are known to be susceptible to produce low-quality data since they lack the interviewer feedback to help clarify the questions when respondents do not understand them. As another example, it is known that computer-based surveys, such as CASI or ACASI, are mostly completed by younger, more computer savvy respondents, which potentially could introduce bias to estimates. T-ACASI, on the other hand, mainly suffers from high break-offs. There are additional issues about the feasibility of utilizing T-ACASI in survey tools with the elderly [12]. In addition, when surveying disadvantaged populations, self-administered surveys might not be a viable option. In fact, illiteracy, poor vision, respondent preference, or other reasons can cause self-administration not to occur: in a self-administered component of a computer-assisted personal survey, only 79% of CASI cases were actually fully self-administered [13]. For an extensive review of advantages and disadvantages of some of the common survey modes, see Smith and Kim [14].
\nAn effective, alternative way to improve response rates and prevent SDB simultaneously is to increase the perceived privacy of the respondents. If the respondents’ privacy can be guaranteed, then their tendency to refuse to participate and/or provide untruthful answers would decrease. All indirect questioning techniques aim to achieve this goal via different approaches. In the next section, we review some of the indirect questioning techniques that have been developed to increase the perceived privacy of the respondents, where the characteristic under study (the outcome) is binary in nature. Some of these techniques explained here have been extended to the cases where the characteristic under study is quantitative or polychotomous in nature; here we will only focus on the binary outcomes, such as in yes/no type of questions. Note that all indirect questioning techniques have produced extensive research areas: they all have been modified and/or extended since they have been first introduced; here we briefly summarize the most important ones and present their main aspects for conciseness.
\nSeveral indirect surveying methodologies have been developed to increase respondents’ confidentiality when the characteristic under study has a sensitive nature. Among them, the most commonly used ones for binary outcomes are, namely, unmatched count technique (UCT), network scale-up technique (NST), nonrandomized response technique (NRRT), and randomized response technique (RRT).
\nUCT, which is also called the item count technique, was first introduced by Raghavarao and Federer [15] with the name “block total response procedure,” but it was formally developed by Miller [16] in the form that we use today. Since then, UCT has been applied by many researchers such as Miller et al. [17], LaBrie and Earleywine [18], Biemer and Brown [19], Wolter and Laier [20], Gervais and Najle [21], and so forth. UCT provides privacy by embedding a sensitive behavior (which is of interest) within several nonsensitive behaviors. All nonsensitive behaviors and sensitive behavior should be binary outcomes (yes/no). In applying the technique, survey participants are randomly divided into two groups. Individuals in one group are provided with a list of nonsensitive behaviors (say, k items), whereas individuals in the other group are provided with the same list of nonsensitive behaviors plus one sensitive behavior that is under study (in total k + 1 items). Participants in both groups are asked to report the total number of activities that they have engaged in. The prevalence of the sensitive behavior is then estimated by calculating the difference between the two independent group means. Several researchers have modified and/or extended UCT in recent years such as Tsuchiya [22], Chaudhuri and Christofides [23], Hussain et al. [24], Ibrahim [25], and so on. As an example on how to apply UCT, consider the study of Zimmerman and Langer [26] in which the technique was utilized to improve the prevalence estimates of marihuana use and ever having had sex with a person of the same gender among the tenth grade students in the Miami-Dade County Public Schools. In their study, the sample (1524 students) was randomly assigned to receive one of three lists on the survey: 33% of the respondents received a list with four nonsensitive items only; 33% received a list with the four nonsensitive items plus the sensitive item about sex with someone of the same gender; 33% received a list with the four nonsensitive items plus the sensitive item about ever using marihuana. Their UCT estimate of prevalence of having sex with someone of the same gender was 80% higher than the prevalence from direct questioning (DQ) (15.9 vs. 8.7%); similarly, their UCT estimate of marihuana use was 21% higher than the prevalence from DQ (20.6 vs. 16.7%). Assuming that for socially undesirable behaviors, higher prevalence estimates are more accurate than the lower prevalence estimates; Zimmerman and Langer [26] concluded that their results demonstrate the superiority of UCT compared to DQ.
\nThe NST was first proposed by Bernard et al. [27] in order to estimate the size of a population at risk and was first used to get an estimate of the number of victims killed in the 1985 Mexico City earthquake [28]. The method was later refined and used to estimate the HIV-seropositive persons in the USA [29]. NST basically involves two steps: (1) the personal network size of the members of a random sample of a population is estimated and (2) an estimate of the number of members of the hidden subpopulation is obtained using the information from step 1. The method heavily relies on the assumption that people’s social networks on average are representative of the general population; for example, if respondents report knowing 500 people on average, five of whom are sex workers, we can estimate that 1% of the general population is sex workers. The estimated prevalence is then combined with known information about the size of the general population, say the population of the USA, to produce an estimate for the number of people in the USA who are sex workers (see Russell et al. [30] for more details on NST and its limitations).
\nNRRT was first introduced by Swensson [31] and later modified by Takahasi and Sakasegawa [32]. The main idea behind Swensson’s NRRT was to combine a nonsensitive behavior with a sensitive behavior in the same question so that it would not be possible for the interviewer to know which behavior is being responded with a “yes” answer; and therefore, respondents are provided with some level of privacy. Swensson’s NRRT requires two independent samples to calculate the estimate of the sensitive characteristic; for this purpose, survey participants can be randomly divided into two groups. Let U be the nonsensitive behavior, such as being married, and let A be the sensitive behavior under study, such as abusing prescription drugs. Let us demonstrate the combined question using Table 1 given below.
\nA (Do you use prescription pain relievers without a doctor’s prescription?) | \nU (Are you married?) | \n|
---|---|---|
Yes | \nNo | \n|
Yes | \na | \nb | \n
No | \nc | \nd | \n
Demonstration of Swensson’s NRRT.
Respondents in the first group receive the question “Do you belong to one of the groups a, b, or c in the table?” whereas respondents in the second group receive the question “Do you belong to one of the groups a, b, or d in the table?” Realize that the probability of belonging to groups a, b, c, or d is P (A = 1, U = 1), P(A = 1, U = 0), P(A = 0, U = 1), or P(A = 0, U = 0), respectively. If we denote the unknown proportion of the population members who have the sensitive characteristic A, i.e., the prevalence of the sensitive characteristic, by \n
where \n
and the probability of getting a “yes” response from sample 2 becomes
\nSince,
\nand
\nusing the Eqs. (1) and (2), we can write
\nor
\nFrom Eq. (3), \n
where \n
The variance of the estimator given in Eq. (4) is derived in a few steps:
\nwhich can be estimated by
\nSwensson’s NRRT was later modified by Takahasi and Sakasegawa [32] as follows: In the first stage, all respondents are asked a nonsensitive binary question, such as “If you have to choose between adopting a cat or a dog, which would you prefer?” but directed not to report their answers to the interviewer (replies are silent). In the second stage, the sensitive behavior is combined with the previous nonsensitive question and asked the respondents in the format given below:
If you are a dog person, and use prescription pain relievers without a doctor?s prescription, say 0.
If you are a dog person, and do not use prescription pain relievers without a doctor?s prescription, say 1.
If you are a cat person, and use prescription pain relievers without a doctor?s prescription, say 1.
If you are a cat person, and do not use prescription pain relievers without a doctor?s prescription, say 0.
In this NRRT, to be able to obtain the estimates, the nonsensitive and sensitive behaviors need to be independent (U and A should not be related). As we explain in the next section, if the nonsensitive binary question’s prevalence in the population is known, then Takahasi and Sakasegawa’s NRRT is equivalent to Warner’s model. If the nonsensitive binary question’s prevalence in the population is not known, then this method requires the use of two independent samples. By relaxing the assumption of independence of the nonsensitive and sensitive behaviors, Takahasi and Sakasegawa [32] proposed an additional NRRT as well, where the nonsensitive behavior has three outcomes instead of two; as a result, in this NRRT, three independent samples are required instead of two independent samples. For a comprehensive review of NRRTs, interested readers are referred to Tian and Tang [33].
\nDifferent than the previous indirect questioning techniques, RRTs provide confidentiality by utilizing a randomization device, such as a deck of playing cards, a pair of dice, or a spinning game wheel while asking the sensitive question. The interviewer does not observe which playing card is chosen or what numbers the dice show, thus a respondent’s privacy is absolutely guaranteed by the RRT process because the interviewer cannot know which statement the participant is responding to. In the next section, we review some of the main RRTs that have been proposed as well as some of the recently developed techniques.
\nThe first RRT was introduced by Warner [34]. Warner’s RRT asks the sensitive question by providing respondents a randomization device with two statements on it that appear with known probabilities θ and 1−θ. For example, consider a spinning game wheel which divided into two sectors with areas θ and 1−θ. The first statement on the device possesses the sensitive characteristic, and the other statement is simply the complementary of the first one. Let us suppose that the sensitive characteristic is being HIV+. The two statements on the wheel would read “I am HIV+” and “I am HIV-” (see Figure 1). The respondents spin the wheel in private and answer truthfully with a “yes” or “no” to the statement on which the arrowhead lands. Since the spinning process is not observed by the interviewer, this model assures privacy protection for the respondents [34].
\nDemonstration of the randomization device in the Warner’s model.
Let the unknown proportion of the population members who have the sensitive characteristic A be denoted by \n
where \n
and, from Eq. (7), an unbiased estimator of \n
where \n
Now, let us compare Swensson’s NRRT with Warner’s model. For simplicity, let us assume that \n
and
\nrespectively, assuming that the nonsensitive and sensitive behaviors are independent. Since we have
\nand
\nthe variance of \n
In order to compare Warner’s RRT with Swensson’s NRRT, we calculated theoretical relative efficiencies (REs)
\nfrom Eqs. (8) and (9) for various combinations of \n
πA | \n\n\n | \n||||||||
---|---|---|---|---|---|---|---|---|---|
0.05 | \n0.10 | \n0.15 | \n0.20 | \n0.25 | \n0.30 | \n0.35 | \n0.40 | \n0.45 | \n|
0.1 | \n0.445 | \n0.489 | \n0.590 | \n0.765 | \n1.067 | \n1.630 | \n2.854 | \n6.360 | \n25.298 | \n
0.2 | \n0.495 | \n0.546 | \n0.650 | \n0.828 | \n1.138 | \n1.717 | \n2.978 | \n6.592 | \n26.122 | \n
0.3 | \n0.524 | \n0.588 | \n0.702 | \n0.892 | \n1.219 | \n1.831 | \n3.162 | \n6.974 | \n27.577 | \n
0.4 | \n0.545 | \n0.624 | \n0.754 | \n0.963 | \n1.320 | \n1.984 | \n3.427 | \n7.558 | \n29.878 | \n
0.5 | \n0.564 | \n0.662 | \n0.813 | \n1.052 | \n1.455 | \n2.201 | \n3.818 | \n8.446 | \n33.445 | \n
0.6 | \n0.585 | \n0.708 | \n0.891 | \n1.175 | \n1.650 | \n2.527 | \n4.424 | \n9.848 | \n39.145 | \n
0.7 | \n0.615 | \n0.775 | \n1.009 | \n1.370 | \n1.969 | \n3.072 | \n5.455 | \n12.263 | \n49.028 | \n
0.8 | \n0.667 | \n0.899 | \n1.234 | \n1.749 | \n2.600 | \n4.164 | \n7.541 | \n17.188 | \n69.271 | \n
0.9 | \n0.817 | \n1.256 | \n1.892 | \n2.867 | \n4.480 | \n7.444 | \n13.843 | \n32.120 | \n130.806 | \n
Relative efficiencies of the estimators from Warner’s model and Swensson’s NRRT for various \n
One can conclude from Table 2 that Warner’s model is more efficient, i.e., has smaller variance, than Swensson’s NRRT for small \n
p | \n\n\n | \n||||||||
---|---|---|---|---|---|---|---|---|---|
0.05 | \n0.10 | \n0.15 | \n0.20 | \n0.25 | \n0.30 | \n0.35 | \n0.40 | \n0.45 | \n|
πA = 0.1 | \n|||||||||
0.05 | \n0.445 | \n0.691 | \n1.049 | \n1.601 | \n2.516 | \n4.200 | \n7.840 | \n18.239 | \n74.394 | \n
0.10 | \n0.315 | \n0.489 | \n0.743 | \n1.133 | \n1.781 | \n2.974 | \n5.551 | \n12.913 | \n52.672 | \n
0.15 | \n0.251 | \n0.389 | \n0.590 | \n0.901 | \n1.416 | \n2.365 | \n4.414 | \n10.268 | \n41.882 | \n
0.20 | \n0.213 | \n0.330 | \n0.501 | \n0.765 | \n1.203 | \n2.008 | \n3.748 | \n8.720 | \n35.567 | \n
0.25 | \n0.189 | \n0.293 | \n0.445 | \n0.679 | \n1.067 | \n1.781 | \n3.324 | \n7.733 | \n31.543 | \n
0.30 | \n0.173 | \n0.268 | \n0.407 | \n0.621 | \n0.976 | \n1.630 | \n3.043 | \n7.078 | \n28.870 | \n
0.35 | \n0.162 | \n0.251 | \n0.382 | \n0.583 | \n0.916 | \n1.529 | \n2.854 | \n6.640 | \n27.085 | \n
0.40 | \n0.155 | \n0.241 | \n0.366 | \n0.558 | \n0.877 | \n1.465 | \n2.734 | \n6.360 | \n25.940 | \n
0.45 | \n0.151 | \n0.235 | \n0.357 | \n0.544 | \n0.855 | \n1.428 | \n2.666 | \n6.202 | \n25.298 | \n
0.50 | \n0.150 | \n0.233 | \n0.354 | \n0.540 | \n0.848 | \n1.417 | \n2.644 | \n6.152 | \n25.091 | \n
πA = 0.2 | \n|||||||||
0.05 | \n0.495 | \n0.681 | \n0.952 | \n1.369 | \n2.061 | \n3.334 | \n6.086 | \n13.949 | \n56.409 | \n
0.10 | \n0.397 | \n0.546 | \n0.763 | \n1.098 | \n1.653 | \n2.675 | \n4.883 | \n11.192 | \n45.258 | \n
0.15 | \n0.338 | \n0.465 | \n0.650 | \n0.935 | \n1.408 | \n2.278 | \n4.158 | \n9.530 | \n38.537 | \n
0.20 | \n0.300 | \n0.412 | \n0.576 | \n0.828 | \n1.247 | \n2.018 | \n3.684 | \n8.443 | \n34.142 | \n
0.25 | \n0.273 | \n0.376 | \n0.525 | \n0.756 | \n1.138 | \n1.841 | \n3.360 | \n7.700 | \n31.138 | \n
0.30 | \n0.255 | \n0.351 | \n0.490 | \n0.705 | \n1.061 | \n1.717 | \n3.134 | \n7.183 | \n29.046 | \n
0.35 | \n0.242 | \n0.333 | \n0.466 | \n0.670 | \n1.008 | \n1.632 | \n2.978 | \n6.826 | \n27.604 | \n
0.40 | \n0.234 | \n0.322 | \n0.450 | \n0.647 | \n0.974 | \n1.576 | \n2.876 | \n6.592 | \n26.659 | \n
0.45 | \n0.229 | \n0.315 | \n0.441 | \n0.634 | \n0.954 | \n1.544 | \n2.819 | \n6.460 | \n26.122 | \n
0.50 | \n0.228 | \n0.313 | \n0.438 | \n0.630 | \n0.948 | \n1.534 | \n2.800 | \n6.417 | \n25.948 | \n
πA = 0.3 | \n|||||||||
0.05 | \n0.524 | \n0.683 | \n0.916 | \n1.275 | \n1.871 | \n2.967 | \n5.336 | \n12.103 | \n48.646 | \n
0.10 | \n0.450 | \n0.588 | \n0.788 | \n1.097 | \n1.610 | \n2.553 | \n4.591 | \n10.412 | \n41.851 | \n
0.15 | \n0.401 | \n0.523 | \n0.702 | \n0.977 | \n1.433 | \n2.273 | \n4.087 | \n9.270 | \n37.259 | \n
0.20 | \n0.366 | \n0.478 | \n0.641 | \n0.892 | \n1.309 | \n2.075 | \n3.732 | \n8.465 | \n34.024 | \n
0.25 | \n0.341 | \n0.445 | \n0.597 | \n0.831 | \n1.219 | \n1.933 | \n3.477 | \n7.886 | \n31.695 | \n
0.30 | \n0.323 | \n0.422 | \n0.565 | \n0.787 | \n1.154 | \n1.831 | \n3.292 | \n7.468 | \n30.014 | \n
0.35 | \n0.310 | \n0.405 | \n0.543 | \n0.756 | \n1.109 | \n1.758 | \n3.162 | \n7.172 | \n28.826 | \n
0.40 | \n0.302 | \n0.394 | \n0.528 | \n0.735 | \n1.078 | \n1.710 | \n3.075 | \n6.974 | \n28.032 | \n
0.45 | \n0.297 | \n0.387 | \n0.520 | \n0.723 | \n1.061 | \n1.682 | \n3.025 | \n6.861 | \n27.577 | \n
0.50 | \n0.295 | \n0.385 | \n0.517 | \n0.719 | \n1.055 | \n1.673 | \n3.009 | \n6.824 | \n27.429 | \n
Relative efficiencies of the estimators from Warner’s model and Swensson’s NRRT for various \n
The FORTRAN code used for Table 3 can be obtained from the author upon request.
\nOne can observe from Table 3 that Warner’s model is more efficient than Swensson’s NRRT only for small \n
When the nonsensitive binary question’s prevalence in the population is known (say, the prevalence of being a dog person is \n
which is equal to the probability of getting a “yes” response from Warner’s model, i.e., Eq. (7) and thus, provides the same estimator when solved for \n
There have been many different RRTs developed since Warner’s original method, such as in Greenberg et al. [36, 37], Gupta [38], Gupta et al. [39, 40, 41], Yu et al. [42], Sihm et al. [43], Gupta and Shabbir [44], and so on. Efforts specifically have been made to improve the efficiency of the technique by reducing the variance and thus the confidence intervals, because, the primary disadvantage of the Warner’s model, and in fact of all RRTs, is that the variances of the estimators are higher than the ones that could be obtained from DQ [35, 45]; for a comprehensive review of RRTs, interested readers are referred to Chaudhuri and Mukerjee [35], Chaudhuri [46], and Chaudhuri and Christofides [47]. In the next subsection, we will review some real-life applications of RRTs and their comparisons with other surveying techniques.
\nTwo meta-analyses of 6 validation and 32 comparative studies which utilized RRTs showed that in various settings, the RRT results are superior to those from DQ and become more valid as the sensitivity of a topic increases [48].
\nThe benefits of the RRTs have also been demonstrated by many statistical methodology researchers via theorems and simulation studies; however, their use in large or national surveys has been somewhat limited. In fact, to our knowledge, the only study which applied an RRT on a national level was done by Kirtadze et al. [49] in the country of Georgia. Kirtadze et al. [49] used a multistage cluster sampling and surveyed 4805 respondents to assess under-reporting of drug abuse in the Republic of Georgia. They utilized the unrelated question RRT to ask questions such as “During the last 12 months, have you taken hashish or marihuana?” They found that all RRT estimates for prevalence of controlled substance use were higher than the DQ estimates, which indicates under-reporting with DQ. For example, lifetime cannabis use estimate was 88.24% higher from RRT than from DQ. Kirtadze et al. [49], however, did not use a gold standard such as urinalysis and thus did not know the “true” value of prevalence of illegal drug use in the Republic of Georgia’s study population.
\nAlthough not nationwide, there have been other researchers who incorporated RRTs in their surveys. Fisher et al. [50], for example, used forced RRT to estimate the prevalence of substance use and sexual activity of high school students who enrolled to their clinic. They compared their results with the ones from a non-anonymous questionnaire which was completed by the same students earlier the same academic year. While RRT provided higher rates for substance use-related questions with respect to the DQ, it provided similar rates for sexual activity-related questions (36% from DQ vs. 31% from RRT). Fisher et al. [50] concluded that admitting to sexual activity in the school setting might carry less stigma and perceived risk than admitting to marihuana or cocaine use [50]. We suggest, however, that this result might indicate that the high school students who participated in the study overestimated their sexual behavior when asked directly to live up to peer acceptance; in other words, we suggest that forced RRT corrected the over-reporting.
\nIn another study, Srivastava et al. [51] used Warner’s RRT to assess the extent of sexual abuse among children in several districts of Uttar Pradesh state of India. They found that the estimates from RRT were higher than the national estimates obtained from Ministry of Women and Child Development, Government of India, which is an indicator of potential under-reporting with DQ.
\nIn a more recent study, Chhabra et al. [52] used convenience sampling and asked the question “Have you ever been a victim of sexual abuse by a friend or family member?” to 585 students in a college in Delhi, India. They divided their sample into three equal randomly selected groups and asked the sexual abuse-related question using (1) DQ, (2) the RRT proposed by Sihm et al. [43], and (3) the confidential method, which was their gold standard to compare their results. The prevalence of sexual abuse was 14% with the gold standard, 8% with the DQ method, and 12% with the RRT. Note that their confidential method, however, was also a surveying technique in which the participants wrote down their answers and put them into a closed box.
\nAlthough all RRTs lead to unbiased (i.e., accurate) estimates of the sensitive characteristic of interest, their variances are larger than the ones from the DQ technique. Thus, the price for using an RRT instead of the DQ is the inflated variance, which is due to the randomization process. Consequently, if the question of interest is not considered to be really sensitive by most of the respondents in a specific population, using an RRT instead of the DQ inflates the variance of the estimates unnecessarily. Besides, it is known that there are cultural or social differences in the extent to which topics are perceived as sensitive. For example, smoking marihuana is a less threatening topic in the Netherlands than in the USA, or questions regarding education are considered to be sensitive in Sweden [1]. Similarly, questions regarding HIV status or sexual practices might not be considered to be sensitive by patients who visit an HIV clinic for treatment. Unfortunately, once an RRT is incorporated within a survey, even if the question of interest turns out to be not sensitive after collecting the data, one has to proceed with the inefficient estimate obtained from the RRT. Motivated by the fact that if researchers do not have a priori knowledge about the sensitivity level of a question in a specific population, then they should be able to select between the estimators from an RRT and the DQ; Ardah and Oral [45] proposed a novel two-stage RRT for a binary response where they utilized Warner’s RRT in the second stage. Their model provides unbiased estimators of both prevalence of the sensitive characteristic and the proportion of cheating in the population simultaneously and allows one to obtain better estimates by avoiding the unnecessary penalty, i.e., the inflated variance, if the question of interest turns out to be significantly not sensitive. Although there are some other RRTs which can estimate the sensitivity level of a question, such as in Gupta [38], none of these RRTs have the ability to avoid the inflated variance if the question’s sensitivity level turns out to be low.
\nArdah and Oral [45] denoted the unknown true proportion of population members that have the sensitive characteristic A by \n
where \n
Numerous indirect questioning techniques have been developed to ask survey questions on sensitive topics or stigmatizing characteristics. All indirect questioning techniques have their own limitations: In applying the UCT, only one of the group members provide the information on the sensitive characteristic of interest [25]. NST is known to suffer from recall bias, barrier effects, transmission error, and response bias [54]. NRRTs can be vulnerable to cheating due to distrust as much as the RRTs [55]. RRTs have some disadvantages as well: integrating a randomization device into a survey tool might not be practical in some situations, such as when researchers plan to use venue sampling to reach LGBT community members in gay bars or clubs. RRTs are also known not to work well if the respondents do not understand the process and/or do not follow the instructions properly. Besides, there might be cultural, social, or personal differences in the extent to which topics are perceived to be sensitive. Thus, we suggest that researchers should select the optimal surveying technique by considering various aspects of their study, such as the target population, sensitivity level of the question, available resources, and practicality of integrating a specific technique, at once. As in Erdmann [55], we also suggest that researchers should not rely on the more-is-better assumption, which is assuming that the higher prevalence estimates are more accurate than the lower prevalence estimates, in comparing different techniques; instead, we suggest to use a valid gold standard (such as urinalysis or a lie detector) for comparisons, whenever possible, perhaps using a small subsample.
\n!***************************************************************************
\n! This code was written to calculate the relative efficiencies in Table 2
\n!***************************************************************************
\nINCLUDE \'link_fnl_static.h\'
\nREAL(8) THETA,C, PIA, K,E, VAR_RRT, VAR_NRRT
\nREAL(8) R(21,21)
\nINTEGER I,J,ITENO,N
\nOPEN (3,FILE="C:\\Users\\Oral\\Documents\\Fortran results\\Table2.txt")
\nWRITE(3,*) ""
\nWRITE(3,*) ""
\nWRITE(3,50) "Calculated Relative Efficiencies for various p=theta and Population Proportion (Pi_A) combinations"
\nWRITE(3,*)""
\nWRITE(3,*)"*****RE MATRIX*****"
\nWRITE(3,*)""
\nWRITE(3,*)"p=Theta value "
\nDO K=0.0,1.05,0.05
\nWRITE(3, 100,advance=\'no\') K
\nEND DO
\nWRITE(3, *) "
\nDO J=1,148
\nWRITE(3, 200,advance=\'no\') \'_\'
\nEND DO
\nWRITE(3, *) "
\nTHETA=0.0
\nPIA=0.0
\nDO I=1,11
\nTHETA=0.0
\nDO J=1,21
\nWRITE (*,*) \'theta=p=\', THETA, \'Pi_A=\', PIA
\nVAR_RRT=(PIA*(1-PIA))+((THETA*(1-THETA))/(((2*THETA)-1)**2.0))
\nVAR_NRRT=2*((((PIA*(1-PIA)))*(1-(2*THETA)+(2*(THETA**2.0))))+(2*(1-PIA)*THETA*(1-THETA)))
\nWRITE (*,*) \'VAR_RRT=\',VAR_RRT, \'VAR_NRRT=\', VAR_NRRT
\nR(I,J)=VAR_RRT/VAR_NRRT
\nTHETA=THETA+0.05
\nWRITE(3,100,advance=\'no\') R(I,J);
\nEND DO
\nWRITE (*,*)"
\nWRITE(3, *) "
\nPIA=PIA+0.1
\nEND DO
\n100 FORMAT (F15.5,1X)
\n200 FORMAT (A1)
\nCLOSE(3)
\nEND
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